Ethenoxy n-monoethanolamides of tall oil



United States Patent ETHENOXY N-MONOETHANOLAMIDES 0F TALL OIL Joseph J.Carnes, Stamford, Conn., and William T. Booth, In, Pittsburgh, Pa.,assignors toAmerican Cyanamld Company, New York, N. Y., a corporation ofMaine No Drawing. Original application August 4, 1950, Serial No.177,776. Divided and this application September 13, 1952, Serial No.309,558

5 Claims. c1. zen-97.5

This invention relates to a novel class of nonionic surface-activeagents and to methods for the preparationthereof. More specifically, theinvention is directed to the production of ethenoxy N-monoethanolamidesof tall oil acid mixtures, these being new compositions of matter havinggood wetting and detergent properties.

As is well known, ordinary tall oil is a mixture consistingpredominantly of abietic or rosin acid and higher fatty acidsmost ofwhich are of about 16-18 carbon atoms together with about 5-10% ofunsaponifiables. Mixtures of this type containing from about 30% to 60%by weight of abietic acid and about 40% to 60% of fatty acids representthe ordinarytall oil of commerce. Socalled crude tall oils contain, inaddition to the indicated quantities of abietic and fatty acids, about57% of unsaponifiables, mostof which are lignins and sterols. Refinedtalloilsf are obtained from these crudes by any of several purificationmethods; inmost cases the crude is extracted with a solvent or subjectedto vacuum steam distillation or both. Wh'e'n distillation processes areemployed the ratio of fattyacids to abietic acid can of course bealtered by fractionation,'and compositions containing as little as 20%ofabietic acid and as much as 80% of higher fatty acids are commerciallyavailable. These mixtures constitute the starting materials for use inpreparing the novel compositions of the present in- VCIllIlOIl. r n

We have prepared monoethanolamides of acids from, crude tall oil andrefined tall oil, and have condensed these monoethanolamides withethylene oxide. The resulting ethenoxy N-monoethanolarnides have beenevaluated as wetting agents and as detergents for cotton and woolentextiles. By this means We have found that ethenoxy N-monoethanolamidesof the class described containing from about 4 to about 50 mols ofcombined ethylene oxide per mol of monoethanolamide possess goodsoftening, Wetting and detergent properties and can be used commerciallyas nonionic surface-active agents for these purposes.

The importance of this discovery will be apparent to those familiar withthe Wetting agents and detergents now on the market. Most of these areobtained either from fatty acid triglycerides, which are highlystrategic materials in war time, or from coal tar or petroleumderivatives such as benzene ortoluene which require high temperaturesulfonation procedures in acid resistant equipment. The presentinvention, on the other hand, employs raw materials which are very cheapand abundant and require no specialized or acid-proof manufacturingequipment. 011 the contrary, crude tall oil is the cheapest and mostabundant known source of organic acids,

A and it is most remarkable that high grade Wetting agents anddetergents can be prepared from such a crude and readily availablematerial.

Although useful wetting agents and detergents are obtainable fromethenoxy N-monoethanolamides of tall oil acids when these compoundscontain from 4 to about 50 v 2,744,888 Patented May 8, 1956 2 ethenoxygroups per molecule, we find that improved detergency is obtained inthose compounds containing from about 8 to about 25 mols of combinedethylene oxide. Thus, for example, the detergency of ethenoxyderivatives of crude tall oil and abietic acid ethanolamides on wool andon cotton percale at a concentration of 0.25% active detergent is givenin the following table:

Detergency On Mols Combined Ethylene Oxide Cotton Wool The detergencyvalues given above represent the percent return to original reflectanceof samples impregnated with a standard soil composed of carbon black,lard and hydrocarbon oil after three 20-minute soapings at 130 F. inaccordance with the standard A. A. T. C. C. method. The results showthat a high degree of detergency is possessed by those productscontaining from 8 to 30 mols of combined ethylene oxide per mol ofethanolamide, but the product containing only 4 mols of combinedethylene oxide had little or no detergency. The table also shows thatmaximum detergency on cotton is obtained when condensation productscontaining from 12 to about 20 mols of combined ethylene oxide are used.I

The method of preparing our-new compositionsconsists generally in thesteps of first reacting the desired tall oil mixture withmonoethanolamine in substantially equimolecular quantities attemperaturessufiiciently high to produce the monoethanolamide, followedby condensation with ethylene oxide. n

We find that the best method of producing the N-mono- I ethanolamides oftall oil fatty acid-abietic acid mixtures consists in preparing asolvent-free mixture of the reagents containing an equimolecularquantity plus a small excess of monoethanolamine on the order of 3-10%and heating this mixture at' its boiling point (140200 C.) atatmospheric pressure while condensing and removing the water formed bythe reaction. After the water evolution has ceased the heating iscontinued for an additional l-2 hours, or until titration of a sample ofthe reaction shows a free acid content of less than 3%, calculated asabietic acid. A vacuum is then applied to the reaction mixture and theexcess monoethanolamine is distilled from the product. j

Condensation of ethylene oxide with the monoethanol amides prepared asdescribed above is preferably carried out in the presence of an alkalinecatalyst at elevated temperatures on the order of -150" C. and, ifdesired, under the corresponding superatmospheric pressures. Althoughany suitable alkaline catalyst may be employed such as sodiumalcoholate, sodium or potassium hydroxide, aliphatic amines of 24 carbonatoms such as monoor diethylamine, propylamine or butylamine, or even insome cases an excess of monoethanolamine, we prefer to employ sodiumhydroxide as the catalyst as it is both cheap and efiicient. Theethenoxy derivatives of the N-ethanolamides of crude and refined talloils are most convenientlypreparedby adding about 5 mol percent of thecatalyst, heating the monoethanolamide to about C. in a reaction vesselprovided with an agitator and surmounted by a condenser, and introducingthe desired quantity of ethylene oxide at a reaction temperature of120-150 C. and at such a rate as to maintain a slow reflux. After theethylene oxide introduction is completed the reaction mixture ispreferably agitated for an additional /1 hour to ensure completion ofthe addition reaction.

The new condensation products of our invention vary in form from liquidsof low water solubility to soft, waxy solids which give clear aqueoussolutions. The compounds prepared from crude and purified tall oils andwhich contain from 8 mols or less to about 16 mols of combined ethyleneoxide are heavy syrups which vary in color from dark brown to lightamber, depending on whether crude or purified tall oil is used. Thoseproducts containing 16 to about 30 mols of combined ethylene oxide aredark brown pastes. The products containing from 30-50 mols and more ofcombined ethylene oxide are solids.

tially complete amide formation, without the necessity of a large excessof monoethanolamine, was finally developed. The tall oil or otherabietic acid-fatty acid mixture and an equimolecular quantity ofethanolamine plus a excess were charged into a reaction vessel fittedwith an agitator and a distilling tube equipped with a reflux condenser.The mixture, with continuous agitation, was heated at about 200 C. untilno more water distilled. The heating was then continued at the sametemperature for one additional hour. A sample was then withdrawn andtitrated in aqueous alcohol with 0.1 N sodium hydroxide solution. Whenthe reaction product contained less than 3% of acid, calculated asabietic acid, a vacuum was applied and the excess monoethanolamine wasdistilled from the product. ,All ,the N-ethanolamides listed in thefollowing table were prepared by this procedure and contained less than3% of free acid.

TABLE II.-NETHANOLA,MIDES FROM T'ALL OILS Tall 011 No. Tan igigfidig iffi Percent Product A (From Table I) lamine, Hr Yield No. pp 5 GramsMols Mols 277 o. 95 1. 05 7. 0 9'9 2 Greenish amber glass. 1, 026 3 3.15 4. 0 98 3 Viscous syrup. l228 3'33 2'? '2 33 1 6. o. 260 o. a. 1.0 5.5 99 6 Brown paste.

675 1. 97 2. 5. 0 97 7 Semi-solid. 1, 035 3. 0 3. 4. 0 98 8 o.

909 3. 0 3. 3 7.0 97 9 Brown paste. 1, 184 4. 0 4. 2 5. 5 98 10 Tan wax.1, 030 3. 5 3. 68 4. 5 98 11 Do.

The invention will be described in greater detail by the followingexamples which show specific embodiments thereof. It should beunderstood, however, that these examples are given primarily forpurposes of illustration and not by way of limitation, and thatvariations and substitutions of equivalents may be resorted to withinthe scope of the appended claims.

EXAMPLE 1 Preparation of N-ethanolamides These products were condensedwith varying quantities of ethylene oxide to produce the correspondingethenoxy N-ethanolamides, as will be described in subsequent examples.

EXAMPLE 2 Ethylene oxide condensation products of monoethanolamides ofcrude talloils were prepared by the following procedure. TheN-ethanolamide prepared as described in Example 1, and having thecomposition shown in Table II, was charged into a reaction flasktogether with 5 mol percent of 40% aqueous sodium hydroxide solution.The reaction flask was fitted with a stirrer, an icewater cooledcondenser and a gas inlet tube. The ethanolamide was heated to 120 C.and the desired amount of ethylene oxide was added at a reactiontemperature of 120-l40 C. at such a rate as would maintain a slowreflux, the reflux condenser being open to atmospheric pressure. Thereaction was exothermic and very little TABLE I.'IALL OIL COMPOSITIONSEquiva- Percent Percent Percent Composition Supplier's lent Acid FattIodine y Resin Unsaponi- Appearance Deslgnatm Weight Acids 1 Acidsfiable 1. Mixture I 9 292 24 Light amber paste.

Arizona Crude I 342 168 43.8 6.9.... Dark brown mixture.

. Arizona-Crude II. 349 174 44. 7 6.9. Do.

Arizona Crude III. 337 168 47. 9 7.0 Do. Mixture II 3 302 48.1 Lightamber mixture.

Unitol. 343 165 45-51 D0.

Ligrb.-- 345 160-170 45-50 6-9- D0. Induso 180485 57-62 5-7 Light brow-nmixture. Farac I..- 296 189 68 Refined... Golden orange syrup.

' Farae IIi 294 191 do Do.

i mamas by uremia.-

Made by mixing tall oil abietic acid and distilled tall oil fatty acids.

The production of N-monoethanolamides from these crude and :refined talloil and other mixtures of abietic and fatty acids was. not easy. Whenvolatile solvents of the type of xyleneand solvent naphtha were used thefatty acid ethanolarnides were formed, but abietic acidethanolamide-formation was incomplete. This was due to the fact that asthe internal temperature of the reaction mixture was "increasedtheethanolamine and-water produced by the-reactiontweredistilled.

A reaction procedure capable of producing a substan- 75 external heatwas required to maintain a temperature of 130-140 C. in the reactionvessel. When the desired ratio of ethylene oxide to tall oilN-monoethanolamide was approached the flow of ethylene oxide gas wasinterrupted and the reaction mixture was stirred for /2 hour at C. andweighed. Suflicient ethylene oxide was then added slowly to produce thetheoretical Weight of product and the heating and stirring werecontinued until this final increment was combined.

By this procedure it was possible to combine as much as 50 mols ofethylene oxide for each mol of tall oil N- ethanolamide. The quantitiesof the reagents used, the reaction times and the appearance of theproducts are listed in Table III. The products obtained are unusual inthat those containing a relatively high molar ratio of combined ethyleneoxide (20-50 mols and more) are solids whereas the products having alower ratio of combined ethylene oxide are liquids or pastes. This isthe reverse of the results obtained when monoethanolamides of relativelypure abietic acid are used.

TABLE IIL-ETHENOXY N-ETHANOLAMIDES OF CRUDE TALL OI EthanolamideEthylene Oxide R eac- Produet tion Appearance of No. No. M015 Grams Mol.Time, Product (Table Used Used Ratio Hrs.

3 1. 89 2. 0 2. Dark green-brown liquid. 3 0. 6 66 2. 5 2. 5 D0. 3 0. 566 3. 0 3. 25 Do. 3 0. 9 159 4.0 4. 0 Do. 4 0. 75 132 4. 0 6. 0 Do. 3 0.8 211 6.0 7.0 Do. 3 0. 83 295 8. 0 7. 0 Do. 4 0. 66 232 8. 0 6. 5 Do. 30. 77 305 9. 0 7. 3 Do. 3 0. 74 325 8. 5 D0. 4 0. 68 209 10 7. 0 Do. 30. 7 339 11 7. 5 Dark green-brown syrup. 3 0. 65 345 12 7. 5 D0. 4 0. 53278 12 9. 0 Do. 4 0. 4 282 16 8.5 Dark green-brown paste. 3 0. 55 386 1610. 0 D0. 2 0. 55 388 16 9. 0 Do. 7 0. 58 408 16 9. 5 Do. 6 0. 65 458 1610. 0 Do. 3 0. 48 422 20 9. 0 Dark green-brown solid. 4 0. 2 176 20 9. 5Do. 2 0. 6 528 20 13. 5 Do. 7 0. 35 308 20 9. 5 D0. 6 0. 3 264 20 10. 0Do. 2 0. 28 295 24 10. 5 D0. 3 0.20 264 30 9. 5 Dark brown solid. 3 0.23 503 50 15.0 Light brown solid.

EXAMPLE 3 Following the reaction method described in Example 2,N-ethanolamides of refined tall oils were reacted with from 4 mols to 50mols of ethylene oxide. The quantities of reagents, the reaction times,and the appearance of the products are shown in the following table.

TABLE IV.ETHENOXY N-ETHANOLAMIDES OF REFIN ED TALL OILS EthanolamideEthylene Oxide Reac- Prbozduct N M I qtion Apgeariint? o! o. o. o me, rouc (Table $35 gg Ratio Hrs.

1 0. 6 212 8. 0 6. 5 Light-amber syrup. 9 0. 9 317 8. 0 7. 5 Dark brownsyrup. 9 0. 7 370 12 9. 0 Dark brown paste. 5 0. 55 291 12 5. 0Lightamber syrup. 1 0. 35 245 16 8. 5 Do. 10 0. 3 211 16 5. 5 Dark brownpaste.

0 0. 6 423 16 10. 0 Do. 8 0. 55 887 16 10. 0 Do. 10 0. 5 440 20 12. 0Do. 9 0. 5 440 20 12. 0 D0. 8 0. 25 202 20 12. 0 Do. 9 0. 35 462 30 11.5 Light brown solid. 9 0. 25 550 50 14. 0 Do.

This is a division of our copending application Serial No. 177,776 filedAugust 4, 1950, now abandoned.

What we claim is:

l. Ethenoxy N-monoethanolamides of tall oil acid mixtures containingabout 80% to 20% by weight of fatty acids of 16-18 carbon atoms andabout 20% to by weight of abietic acid, said N-monoethanolamidederivatives containing about 4 to 50 ethenoxy groups per molecule.

2. Ethenoxy N-monoethanolamides of tall oil acid mixtures according toclaim 1 and containing from about 8 to 25 ethenoxy groups per molecule.

3. Ethenoxy N-monoethanolamides of crude tall oil acids containing about30% to 60% by weight of abietic acid, about 40% to 60% of fatty acids of16-18 carbon atoms and about 5-10% of unsaponifiables, saidN-monoethanolamide derivatives containing from about 4 to 25 ethenoxygroups per molecule.

4. A method of producing ethenoxy N-monoethanolamides of tall oil acidmixtures which comprises preparing a mixture of tall oil acidscontaining about to 20% by weight of fatty acids of 16-18 carbon atomsand about 20% to 75 by weight of abietic acid and an equimolecularquantity plus a 3-10% excess of monoethanolamine, heating said mixtureat about 200 C. while condensing and removing water, continuing theheating until the reaction product contains less than 3% of acidcalculated as abietic acid, applying a vacuum and distilling excessmonoethanolamine from the product, adding an alkaline condensationcatalyst and introducing ethylene oxide while maintaining an internaltemperature of about -150 C., and continuing the ethylene oxideintroduction until from 4 to about 50 mols per mol of tall oil acidN-monoethanolamide has reacted.

5. A method of producing ethenoxy N-monoethanolamides of tall oil acidmixtures which comprises preparing a solvent-free mixture of tall oilacids containing about 30% to 60% by Weight of abietic acid and about40% to 60% fatty acids of 16-18 carbon atoms and an equimolecularquantity plus a 3-10% excess of monoethanolamine, heating said mixtureat its boiling point at atmospheric pressure while condensing andremoving water, continuing the heating at approximately the sametemperature after water evolution has ceased until the reaction productcontains less than 3 of acid calculated as abietic acid, applying avacuum and distilling excess monoethanolamine from the product, addingan alkaline condensation catalyst and introducing ethylene oxide Whilemaintaining an internal temperature of 100-150" C., and continuing theethylene oxide introduction until from 8 to about 50 mols per mol oftall oil acid N-monoethanolamide has reacted.

References Cited in the file of this patent UNITED STATES PATENTS Re.21,530 Kritehevsky Aug. 13, 1940 2,085,706 Schoeller June 29, 19372,469,493 Barker May 10, 1949 2,520,381 Carnes Aug. 29, 1950 2,555,606Potts June 5, 1951 FOREIGN PATENTS 467,571 Great Britain June 16, 1937

1. ETHENOXY N-MONOETHANOLAMIDES OF TALL OIL ACID MIXTURES CONTAININGABOUT 80% TO 20% BY WEIGHT OF FATTY ACIDS OF 16-18 CARBON ATOMS ANDABOUT 20% TO 75% BY WEIGHT OF ABIETIC ACID, SAID N-MONOETHANOLAMIDEDERIVATIVES CONTAINING ABOUT 4 TO 50 ETHENOXY GROUPS PER MOLECULE.